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CN1292014C - Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material - Google Patents

Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material Download PDF

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Publication number
CN1292014C
CN1292014C CNB2004100843278A CN200410084327A CN1292014C CN 1292014 C CN1292014 C CN 1292014C CN B2004100843278 A CNB2004100843278 A CN B2004100843278A CN 200410084327 A CN200410084327 A CN 200410084327A CN 1292014 C CN1292014 C CN 1292014C
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China
Prior art keywords
polyester
acid
add
glycol
waste material
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Expired - Fee Related
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CNB2004100843278A
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Chinese (zh)
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CN1631935A (en
Inventor
钱建华
刘坐镇
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HUACHANG POLYMER Co Ltd HUADONG TECH UNIV
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HUACHANG POLYMER Co Ltd HUADONG TECH UNIV
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Priority to CNB2004100843278A priority Critical patent/CN1292014C/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/143—Feedstock the feedstock being recycled material, e.g. plastics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

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  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a method for synthesizing p-phenyl unsaturated polyester resin by all kinds of recovered polyester waster, which comprises the following four steps: (1), carrying out alcoholysis and ester exchange reaction for polyester waster and polyatomic alcohol under the condition of catalyst existence; (2), carrying out esterifying polycondensation reaction for an alcoholysis product and unsaturated dibasic acid (or anhydride); (3), using dicyclopentadiene (DCPD) to seal end and modify at the later period of etherification polycondensation; (4), adding a styrene solution into a modified reaction product to crosslink. The method of the present invention has the advantages of wide raw material source, low price, environmental pollution reduction, production cost reduction, time saving, energy saving, etc.; simultaneously, the present invention overcomes the disadvantage of the poor solubility of polyester in styrene.

Description

Synthesis of Polyester Waste with Benzene-Based Unsaturated Polyester Resin
Technical field
The present invention relates to the method for the synthetic terephthalic unsaturated polyester resin of polyester waste material (below be abbreviated as UPR) of the various recovery of a kind of usefulness.
Background technology
Polyester is that the non-fiber applications of polyester develops rapidly in recent years, can be used as packaging vessel, polyester film and engineering plastics such as beverage, food as the development of raw materials of synthon at first.Usually the different steps at polyester production process all produces waste product and scrap stock inevitably, and these polyester waste materials account for the 3-5% of turnout.In the polyester use, nearly all be disposable as wrapping material such as polyester bottles simultaneously, the waste quantity of generation sharply increases.These polyester waste material enormous amount not only can cause great waste if give it up, and can serious environment pollution.How to solve the recycling of useless polyester and utilize the important topic that has become current social.
Usually, UPR is through polycondensation synthetic polymkeric substance by unsaturated dibasic acid or acid anhydrides, monounsaturated dicarboxylic acid or acid anhydrides and dibasic alcohol.In order to obtain ester group and two equally distributed polymkeric substance of key, the industrial production technique that adopts " two step method ".The first step is with monounsaturated dicarboxylic acid or acid anhydrides (as Tetra hydro Phthalic anhydride, m-phthalic acid or terephthalic acid) and dibasic alcohol (as propylene glycol) reaction, when acid number is lower than 10mgKOH/g, most monounsaturated dicarboxylic acids have participated in reaction, and second step was fed into reaction end with unsaturated dibasic acid (as MALEIC ANHYDRIDE) again.The thermotolerance of p-phenyl UPR, erosion resistance, solvent resistance have surpassed metaphenylene UPR, and adjacent especially benzene type UPR is incomparable.The raw material when but p-phenyl UPR produces, terephthalic acid or to contain the reactive behavior of polyester of terephthalic acid very low, must add suitable catalyzer and compressive reaction in the reaction process, simultaneously because the crystallizing polyester that the symmetry of its structure makes tendency is big, place the back polyester and can become opaque, it is higher to add existing explained hereafter cost, so restricted it to a certain extent in industrial application.
Summary of the invention
The purpose of this invention is to provide the method for the synthetic p-phenyl UPR of polyester waste material of the various recovery of a kind of usefulness,, improve the quality of products, overcome unsaturated linear polyester poorly soluble shortcoming in vinylbenzene to reduce production costs.
For realizing purpose of the present invention, adopt the new technological process of production, as shown in Figure 1:
(1) polyester waste material, polyvalent alcohol and catalyzer are dropped in the reactor by proportioning, under nitrogen protection, stir and progressively intensification, between 190-200 ℃, carry out alcoholysis and transesterification reaction, become all even transparent, be the terminal point of alcoholysis until reaction system.
(2) temperature of charge is reduced to below 160 ℃, add unsaturated dibasic acid and be warming up to 190-210 ℃ gradually in system, insulation reaction reaches 80mgKOH/g until acid number.
(3) temperature of charge is reduced to 110-140 ℃ and add phosphoric acid, under refluxing, in 1h, slowly add dicyclopentadiene, behind the insulation 1h, slowly rise to 190-210 ℃, when water outlet reach theoretical aquifer yield 2/3 the time, vacuumize and force moisture to steam, reach 30mgKOH/g until acid number.
(4) be cooled to 180 ℃ and add stopper, then material is cooled off, add styrene solution and control dilution still temperature between 70-90 ℃, fully stir the postcooling filtration and get product.
Wherein the proportioning of each reactant is as follows:
The weight ratio 1 of polyester waste material and polyvalent alcohol: (1.50～7.50);
The weight ratio of polyester waste material and unsaturated dibasic acid is 1: (0.50～5.00);
Alcoholysis and transesterification catalyst add-on are the 0.01%-1.0% of polyester waste material weight;
The mol ratio of total carboxylic acid and polyvalent alcohol is 1: (1.05～1.10);
Total carboxylic acid and dicyclopentadiene mol ratio are 1: (0.10～0.50);
The phosphoric acid add-on is 0～0.1% of a polyester gross weight;
The add-on of stopper is 0.005～0.05% of a polyester gross weight;
Cinnamic add-on is 30～40% of a polyester gross weight.
Polyester waste material of the present invention is meant in the polyester production process and daily life use in polyester tankage, the waste of recyclable utilization, these polyester are linear polymers that terephthalic acid and dibasic alcohol are made: polyethylene terephthalate (abbreviating PET as), Poly(Trimethylene Terephthalate) or polybutylene terephthalate.It is clean that the useless film that produces in the polyester production process, waste silk keep mostly, can be directly used in to produce UPR; The packing articles (bottle, film etc.) of some contaminated waste material and recovery polyester needs could utilize after fragmentation, washing and separating treatment.Polyester waste material in polyvalent alcohol, under alcoholysis conditions from wetting be a process slowly to dissolving, useless polyester granularity helps the carrying out of process for a short time, adopting particle diameter usually is 1-10mm.
The polyvalent alcohol that is applicable to alcoholysis is ethylene glycol normally, propylene glycol, 1,4-butyleneglycol, 1,3 butylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexylene glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 3,3-glycol, glycerol, TriMethylolPropane(TMP), trimethylolethane, tetramethylolmethane etc.Above-mentioned polyvalent alcohol can two or more materials mixture use.When only adopting a kind of polyvalent alcohol, preferably has the unsymmetrical structure polyvalent alcohol.
Add the polyester waste material and the polyvalent alcohol that crush in the reactor in proportion, under agitation heat up gradually, make polyester waste material generation alcoholysis and transesterification reaction, the product of alcoholysis is monomer, dimer and the tetrameric mixture of terephthalic acid dibasic alcohol, has different polyvalent alcohol fragments to depend on the type of used polyvalent alcohol in identical monomer, dimer and the tetramer.The general formula of its reaction is:
R 1--the residue of----polyvalent alcohol except that terminal hydroxy group
N, the polymerization degree of m-----polymkeric substance.
Can select for use catalyzer to quicken depolymerization reaction when alcoholysis and transesterification reaction, catalyzer commonly used can be (1) acetic acid salt, as manganese acetate, zinc acetate, Cobaltous diacetate, calcium acetate, Lithium Acetate, plumbic acetate etc.; (2) titanate ester is as tetrabutyl titanate, titanium isopropylate etc.; (3) organic tin, as oxidation monobutyl tin, dibutyltin oxide, 2 ethyl hexanoic acid monobutyl tin, di-n-butyltin dilaurate, stannous octoate, butyl stannonic acid etc.; (4) antimony is class, as antimonous oxide, and antimony acetate, any one catalyzer in the antimony glycol.Also can be the composite catalyst of above any two kinds or three kinds compositions, preferred catalyzer be an organic tin, and the catalyzer add-on is the 0.01%-1.0% of polyester waste material weight, and optimum amount is 0.1%-0.5%.
When arriving end-point of alcoholysis, alcoholysis product is cooled to 160 ℃ or lower temperature,, makes itself and the reaction of alcoholysis product generation esterifying polycondensation synthesize unsaturated linear polyester to wherein adding unsaturated dibasic acid or acid anhydride.
The esterifying polycondensation reaction expression is:
R 1--the residue of----polyvalent alcohol except that terminal hydroxy group
R 2--the residue of----unsaturated dibasic acid except that the end carboxyl
M, the unsaturated dibasic acid that the polymerization degree of y-----polymkeric substance is used for esterifying polycondensation comprises maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE, cis-methyl-butene diacid, chloro maleic acid or methylene-succinic acid etc.
The present invention adopts dicyclopentadiene to derive from the by product C 5 fraction and coal tar of petroleum cracking system ethene, and its content is more than 78%.The dicyclopentadiene addition can not be too many, otherwise unnecessary DCPD consumes unsaturated double-bond in the polyester molecule chain in the later stage temperature-rise period, makes active decline, and curing speed slows down, and product performance descend.
Stopper comprises Resorcinol, methyl hydroquinone, Tert. Butyl Hydroquinone, tert-butyl catechol, copper naphthenate, benzoquinones, toluene hydroquinone and para benzoquinone etc.
The method according to this invention, the UPR with stability can make in a large number, and production process can be carried out with the common equipment of the universal UPR of preparation.The p-phenyl UPR that the present invention makes compares with existing technology and has the following advantages:
(1) adopts polyester waste material as main raw material, reduced product cost, reduced environmental pollution.
(2) by the modification of dicyclopentadiene blocking method, solved terephthalic unsaturated polyester with cinnamic mutual solubility is poor, final UPR leaves standstill layering afterwards and haze problem.
(3) its goods have good thermotolerance, erosion resistance, solvent resistance, and mechanical mechanics property also is not less than universal UPR, and over-all properties has surpassed metaphenylene UPR.
(4) have good air-drying property and lower cure shrinkage by goods after the modification.
The p-phenyl UPR that the present invention produces has above many premium propertiess, can be widely used in fiber reinforced plastic pipe, storage tank or the equipment lining of various acid-and base-resisting, salt and organic solvent.
Description of drawings
Below in conjunction with accompanying drawing the present invention is made and to further specify:
Fig. 1: Synthesis of Polyester Waste with Benzene-Based Unsaturated Polyester Resin technical process.
Embodiment
Following embodiment will describe the present invention in more detail, but the present invention should not be limited only within these specific embodiments.
Embodiment 1:
Have thermometer at one, agitator in the four-hole boiling flask of nitrogen ingress pipe and fractionation plant, drops into propylene glycol 152g successively, glycol ether 53g, PET polyester bottles fragment (particle diameter is about 5mm) 96g, catalyzer 0.5g.Feed under the situation of nitrogen and be warming up to 190-200 ℃ gradually, the fractionation column temperature is lower than 105 ℃, keeps this temperature all to disappear until the polyester waste material particle, when the reaction system all even gradually transparent terminal point that is alcoholysis that becomes.Temperature of charge is reduced to the 222g of adding below 160 ℃ MALEIC ANHYDRIDE, be warming up to 190-210 ℃ gradually, the fractionation column temperature is lower than 105 ℃, reaches 80mgKOH/g until acid number, temperature of charge is reduced to 110-140 ℃ add the 0.2g phosphoric acid catalyst, under refluxing, in 1h, slowly drip the 30g dicyclopentadiene, the insulation 1h after, slowly rise to 190-210 ℃, when water outlet reach theoretical aquifer yield 2/3 the time, vacuumize and force moisture to steam, reach 30mgKOH/g until acid number and stop to vacuumize.Be cooled to 180 ℃ and add Resorcinol 0.08g, after stirring half an hour, continue to be cooled to and add styrene solution 280g below 120 ℃, fully stirring mixes unsaturated polyester and vinylbenzene, temperature during the control dilution is cooled to 50-60 ℃ of filtration at last and promptly gets the muddy viscous liquid of oyster white at 70-90 ℃.
Embodiment 2:
With 62g ethylene glycol, the 76g propylene glycol, the 53g glycol ether, 8g hexalin, 96g do not have oily terylene waste, and 0.3g esterifying catalyst manganese acetate drops in the four-hole boiling flask shown in the embodiment 1, subsequent step changes MALEIC ANHYDRIDE among the embodiment 1 into FUMARIC ACID TECH GRADE acid anhydride 262g, phosphoric acid changes 0.15g into, and dicyclopentadiene changes 25g into, is undertaken by operation steps similarly to Example 1.
Embodiment 3:
The 1500L reactor has agitator, and temperature shows that fractional column and charging opening pump into the 228kg propylene glycol earlier, the 79.5kg glycol ether in reactor.Liquid ingredient is heated to about 100 ℃, starts stirrer and feed nitrogen, add 144kg PET polyester bottles fragment (particle diameter is about 5mm), esterifying catalyst stannous octoate 2kg closes charging opening behind reinforced the end, continues to stir and heat up.When still temperature rise to 170 ℃ begins that distillate is arranged, control fractionation column temperature is lower than 105 ℃, and write down temperature of reaction and heat up in a steamer a temperature per half an hour in the reaction process.Continue to be warming up to 190-200 ℃, keep this temperature all to disappear until the polyester waste material particle, after 5-6 hour when the reaction system all even gradually transparent terminal point that is alcoholysis that becomes.After the alcoholysis fully material in the reactor is cooled to the 333kg of input below 160 ℃ MALEIC ANHYDRIDE, is warming up to 190-210 ℃ gradually, control fractionation column temperature is lower than 105 ℃, reaches 80mgKOH/g until acid number.Temperature of charge is reduced to 110-140 ℃ add 300g phosphoric acid, under refluxing, in 1h, slowly drip 45kg dicyclopentadiene, insulation 1h, slowly rise to 190-210 ℃, when water outlet reach theoretical aquifer yield 2/3 the time, vacuumize and force moisture to steam, reach 30mgKOH/g until acid number.Reactant is cooled to 180 ℃ adds Resorcinol 0.12kg.Polyester is lowered the temperature gradually, in the dilution still, squeeze into vinylbenzene 420kg in the time of cooling, drive agitator, polyester is put in the dilution still, make temperature be controlled at 70-90 ℃ of stirring, fully stir postcooling and promptly filter blowing, obtain the muddy thick liquid of oyster white with pump.
Embodiment 4:
With the 760kg propylene glycol, the 265kg glycol ether, the 192kg terylene waste material, 5kg composite catalyst (3kg Cobaltous diacetate+2kg butyl (tetra) titanate) drops in the device (5000L) shown in the embodiment 3, subsequent step changes MALEIC ANHYDRIDE among the embodiment 3 into 590kg Tetra hydro Phthalic anhydride and 720kg MALEIC ANHYDRIDE, and phosphoric acid changes 1kg into, dicyclopentadiene 150kg, Resorcinol changes 0.45kg into, and vinylbenzene changes 1550kg into.Undertaken by operation steps similarly to Example 3.
More than among each embodiment the typical quality index of gained polyester as follows:
Index Unit Numerical value Testing method
The resin traditional performance
Outward appearance Oyster white or faint yellow muddy thick liquid
Acid number mgKOH/g 14-20 GB 2895-89
Viscosity (25 ℃) Pa·s 0.30-0.50 GB 7193.1-87
Solids content ％ 59-65 GB 7193.3-87
Gel time (25 ℃) min 16-20 GB 7193.6-87
The casting matrix performance
Flexural strength MPa 72 GB 2570-95
Modulus in flexure GPa 3.8 GB 2570-95
Tensile strength MPa 45 GB 2568-95
Tensile modulus GPa 3.6 GB 2568-95
Heat-drawn wire ℃ 100 GB 1634-89
The glass reinforced plastic performance
Flexural strength MPa 300 GB 2570-95
Annotate: gel time is meant that envrionment temperature is 25 ℃, adds 2.5% methylethyl ketone peroxide, records under the test conditions of 2% cobalt naphthenate solution.

Claims (7)

  1. The method of 1 one kinds of Synthesis of Polyester Waste with Benzene-Based Unsaturated Polyester Resin is characterized in that comprising following four steps:
    (1) polyester waste material, polyvalent alcohol and catalyzer are dropped in the reactor by proportioning, under nitrogen protection, stir and progressively intensification, between 190-200 ℃, carry out alcoholysis and transesterification reaction, become all even transparent, be the terminal point of alcoholysis until reaction system;
    (2) temperature of charge is reduced to below 160 ℃, add unsaturated dibasic acid and be warming up to 190-210 ℃ gradually in system, insulation reaction reaches 80mgKOH/g until acid number;
    (3) temperature of charge is reduced to 110-140 ℃ and add phosphoric acid, under refluxing, in 1h, slowly add dicyclopentadiene, behind the insulation 1h, slowly rise to 190-210 ℃, when water outlet reach theoretical aquifer yield 2/3 the time, vacuumize and force moisture to steam, reach 30mgKOH/g until acid number;
    (4) be cooled to 180 ℃ and add stopper, then material is cooled off, add styrene solution and control dilution still temperature between 70-90 ℃, fully stir the postcooling filtration and get product.
  2. 2 by the described method of claim 1, it is characterized in that the proportioning of described each reactant is as follows:
    The weight ratio 1 of polyester waste material and polyvalent alcohol: (1.50～7.50);
    The weight ratio of polyester waste material and unsaturated dibasic acid is 1: (0.50～5.00);
    Alcoholysis and transesterification catalyst add-on are the 0.01%-1.0% of polyester waste material weight;
    The mol ratio of total carboxylic acid and polyvalent alcohol is 1: (1.05～1.10);
    Total carboxylic acid and dicyclopentadiene mol ratio are 1: (0.10～0.50);
    The phosphoric acid add-on is 0～0.1% of a polyester gross weight;
    The add-on of stopper is 0.005～0.05% of a polyester gross weight;
    Cinnamic add-on is 30～40% of a polyester gross weight.
  3. 3 by the described method of claim 1, it is characterized in that described polyester waste material is the terephthalic acid of recycling from polyester production process and daily life use and the linear polymer that dibasic alcohol is made: polyethylene terephthalate (abbreviating PET as), Poly(Trimethylene Terephthalate) or polybutylene terephthalate.
  4. 4 by the described method of claim 1, it is characterized in that the used catalyzer of described step (1) can be the acetic acid salt, titanate ester, organic tin, antimony is any catalyzer in the class, also can be the composite catalyst of any two kinds or any three kinds of compositions in the above catalyzer.
  5. 5 by the described method of claim 1, it is characterized in that polyvalent alcohol is in the described step (1): ethylene glycol, propylene glycol, 1, the 4-butyleneglycol, 1,3 butylene glycol, glycol ether, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, hexylene glycol, dihydroxyphenyl propane, Hydrogenated Bisphenol A, 3,3-glycol, glycerol, TriMethylolPropane(TMP), trimethylolethane, the mixture of one or more polyvalent alcohols in the tetramethylolmethane.
  6. 6 by the described method of claim 1, it is characterized in that unsaturated dibasic acid is maleic acid, MALEIC ANHYDRIDE, FUMARIC ACID TECH GRADE in the described step (2), cis-methyl-butene diacid, chloro maleic acid or methylene-succinic acid.
  7. 7 by the described method of claim 1, it is characterized in that dicyclopentadiene is a technical grade in the described step (3), and content is more than 78%.
CNB2004100843278A 2004-11-18 2004-11-18 Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material Expired - Fee Related CN1292014C (en)

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